Composite conductive polymer composition, method of manufacturing the same, solution containing the composition, use of the composition

ABSTRACT

The purpose is to provide a technique which enables various kinds of conductive polymer composition to be dissolved in an organic solvent and to be used to form a conductive membrane on a target portion easily. Provided is a composite conductive polymer composition, a method of manufacturing the same, and a solution obtained by dissolving the composition in an aromatic solvent, ester-based solvent or ketone-based solvent. The composition is obtained by doping a π-conjugated polymer (β) with a polymer compound (A), wherein the polymer compound (A) is obtained from (a-1) a monomer having a sulfonic acid group and a polymerizable vinyl group in an amount of 20 to 60 mol %, (a-2) a polar monomer having a hydrophilic group and a polymerizable vinyl group in an amount of 20 to 60 mol %, and (a-3) another polymerizable monomer in an amount of 20 to 60 mol %, and the n-conjugated polymer (β) is obtained from a monomer compound selected from the formulas (I) to (III) 
                         
in the formula (I) to (III), at least one of R 1  to R 4  represent an alkoxy group of C 1  to C 10 , and the other groups represent H, an alkyl group of C 1  to C 10 , or an alkoxy group of C 1  to C 10 ; at least one of R 5  and R 6  represent an alkoxy group of C 1  to C 10 , and the other group represents H, an alkyl group or an alkoxy group of C 1  to C 10 , or R 5  and R 6  jointly represent an alkylenedioxy group of C 1  to C 8 ; and R 7  represents H, an alkyl group of C 1  to C 6 , or an aromatic ring group.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of PCT International PatentApplication No. PCT/JP2010/052353, filed Feb. 17, 2010, and JapanesePatent Application No. 2009-033644, filed Feb. 17, 2009, in the JapaneseIntellectual Property Office, the disclosures of which are incorporatedherein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to a composite conductive polymer composition, amethod of manufacturing the same, a solution containing the composition,and a use of the composition, and more specifically relates to acomposite conductive polymer composition which is obtained by doping,with a polymer compound, a π-conjugated polymer whose monomer componentis aniline, thiophene, pyrrole, or like an aromatic or a heterocycliccompound having an alkoxy group in order to solubilize the π-conjugatedpolymer to a solvent, a method of manufacturing the same, a solutioncontaining the composition, and a use of the composition for anelectrode for a dye-sensitized solar cell or an antistatic film.

2. Description of the Related Art

In order to enhance conductivity of a π-conjugated polymer, it isnecessary to dope the polymer with a dopant. However, the polymer havingextended π-conjugation has high planarity in the polymer chain, and thusthe tendency of the crystallization or stacking of the polymer chains ishigh because of the affinity of the π-bonds. In addition, doping of theπ-conjugated polymer with a dopant enhances the planarity and theaffinity by the π-conjugation, and thus enhances the tendency of thestacking. Therefore, it was a difficult problem to enhance thesolubility (by heat or solvent) of the π-conjugated polymer whileenhancing the electric conductivity.

Here, there has been proposed a polymer in which an alkyl group, analkoxy group, or the like is introduced on the side chain of aπ-conjugated polymer (Patent Document 1). However, doping is necessaryto enhance the electric conductivity to ten to the negative fifth power(s□m) or less, at which the polymer can be called a conductor. Thedoping enhances the planarity and the π-conjugation affinity, and thusthere occurs a problem that sufficient solubility to a solvent cannot beachieved.

In view of the use of the conductive polymer and in view of the easinessof the handling, it is desirable that the polymer is soluble to asolvent or meltable by heat, and in addition a self-supported film orself-supported molded body with sufficient electric conductivity aftermolding or film formation can be obtained. Conventionally, when theseconductive polymers are used, a polymer film is formed on a substrate bydirect electropolymerization or vapor exposure to provide conductivityto the substrate, or thin film polymerization is performed by immersingthe substrate in a solution of an oxidizing agent and a conductivepolymer precursor monomer, followed by heating and so on. Thereafter,the obtained polymer film is processed by doping and so on.

However, the substrate needs to be semiconductor or conductor to performthe electropolymerization, and the corrosion resistance to theelectrolyte is also required, and therefore, the choice of the substrateis limited. Furthermore, the thin film polymerization by direct vaporrequires that an oxidizing agent exists uniformly on a thin film whichis a polymerization field, and is not satisfactory in terms of the filmformation control. In a polymer capacitor application, microasperity isformed on the surface in order to increases the surface area, and it isdifficult to form a conductive polymer on a sufficiently uniformsurface.

There has been proposed several methods of dissolving a conductivepolymer in an organic solvent. Patent Document 2 discloses a method ofmanufacturing poly(3,4-di-substituted thiophene) by use of3,4-di-substituted thiophene, an inorganic ferric salt and an oxidizingagent. Patent Document 3 discloses a water dispersible powder includinga polymer T mainly having repeating thiophene units and at least oneother polyanion polymer P. However, the method in Patent Document 2 is amethod of obtaining powder or a method of performing oxidativepolymerization directly on the target surface, and thus it is impossibleto dissolve the polymer obtained by the method in a solvent or water.Furthermore, the product obtained by the method in Patent Document 3 isjust a water dispersible dispersoid, and is not soluble to an organicsolvent at the molecular level

Furthermore, various researches have been made for more direct method ofnanodispersing to a solvent. Patent Document 4 disclose a method ofproviding a microdispersoid solution at nano level by pulverizingpolyaniline, which is essentially insoluble to a solvent, to nano level,and co-dispersing, to a solvent, the pulverized polyaniline with adispersant of a sulfonic acid anion emulsifier such as SDS(dodecylbenzenesulfonic acid) or PTS (para-toluenesulfonic acid) havinghigh affinity to polyaniline and a solvent. However, the polyaniline isnot substantially dissolved in the solvent, and thus the surface of thecoating film is uneven, and it is not possible to form a self-supportedfilm (also referred to as a homogeneous film. This means a film formedby itself and without forming pinholes), and therefore it is notpossible to form a film after coating unless combined with a binder.

Furthermore, Patent Document 5 discloses a polythiophene solutioncontaining, in water or a mixed solvent of water and an organic solventmiscible to water, polythiophene having a molecular weight of 2,000 to500,000 and obtained by oxidation chemical polymerization in the presentof a polyanion of a polystyrene sulfonic acid, and a polyanion having amolecular weight of 2,000 to 500,000 and derived from a polystyrenesulfonic acid.

The Patent Document proposes a method of manufacturingpoly(ethylenedioxide-substituted thiophene) (PEDOT) which is soluble ordispersible to water or an alcohol solvent by use of oxidativepolymerization in the present of polystyrene sulfonic acid (PSS) and anoxidizing agent. However, the obtained PEDOT/PSS is dispersed in water,but not completely dissolved, and thus it is difficult to suppresspartial stacking between PEDOTs, and therefore dissolution of theconductive polymer was insufficient. In addition, by use of thepolystyrene sulfonic acid shown in the Patent Document, it is difficultto use a solvent other than a solvent having a strong ion dissociationproperty or water. Furthermore, a sulfonic acid group acts as a dopantgroup or a water-soluble functional group, but does not substantiallyhave affinity or compatibility to the monomer. There is no functionalgroup compatible with an alkoxyl group in order to control localizationof an alkoxyl group of an aromatic or a heterocyclic compound, such asaniline, thiophene, or pyrrole, having an alkoxyl group and suppress theplanarity of the π-conjugated polymer. Therefore, sufficient suppressionof the stacking is difficult.

Furthermore, Patent Document 6 disclose a method of forming an organicsolution by performing oxidative polymerization of aniline or anilinederivative in a solvent containing an organic acid or inorganic acid inthe present of a strongly hydrophobic anionic surfactant, followed byprecipitation, isolation, and purification, and thereafter performingextraction by use of an organic solvent immiscible to water.

However, the emulsifier used in the Patent Document is a low-molecularsulfonic acid-based, and aniline is hydrochlorinated beforepolymerization, thereafter the aniline salt is subjected to saltsubstitution by use of a sulfonic acid-based emulsifier. However, inreality, sufficient salt exchange is hard to occur, and thereforepolyanion obtained by the synthetic method of the Patent Document isinsoluble to a solvent, and thus only solvent dispersion in a microdispersing state is obtained, which is problematic. In addition, thesulfonic acid-based emulsifier is used in an equivalent molar amount toaniline, and thus 50% or more of the emulsifier remains unused fordoping, and the unused emulsifier needs to be removed upon use.Therefore, the washing process is complicated, which is problematic.Furthermore, it is very difficult to design the low-molecular emulsifierin a way to introduce a function to enhance solubility to a solution,and a function to suppress the stacking of polyaniline. Even thoughpolyaniline is dissolved temporarily in a solvent, micro-agglomerationdue to the stacking (crystallization of PANI) occurs shortly, which isproblematic. Furthermore, the present inventors conducted the re-testand confirmed that according to the method of the Patent Document, thelocalization of an alkoxyl group in the aniline derivative having analkoxyl group, and chemical and structural relaxation of affinity atquinoimide binding position and amino binding position of thepolyaniline are insufficient, and therefore the stacking is notsuppressed.

Furthermore, Patent Document 7 discloses a method of emulsifying asolution obtained by dissolving, in water or an organic solvent, (A) amonomer having a sulfonic acid functional group and a radicalpolymerizable functional group, and (B) a monomer of aniline or thederivatives thereof; introducing, in the monomer (B), a sulfonic acidstructure derived from the monomer (A), and thereafter polymerize themonomers (A) and (B) in the present of a polymerization initiator toobtain a conductive polymer with the polymer of (B) and the polymer of(B) intertwined.

However, in the method of the Patent Document, because ammoniumpersulfate salt is used as a water-soluble oxidizing agent and a radicalinitiator, it is difficult in reality to obtain the ideal mesh structureof the vinyl-based polymer and polyaniline as mentioned in thespecification. Therefore, according to the method of the PatentDocument, there's a problem in reality that a substantial amount ofvinyl polymer not containing PANI exists, and a dope monomer notincorporated in the vinyl polymer exists in PANI, and thus the obtainedproduct is very nonuniform and unstable.

For example, Patent Document 8 discloses a conductive polyanilinecomposition containing (a) a protonated and substituted or unsubstitutedpolyaniline complex and (b) a compound having a phenolic hydroxyl group,which is dissolved in an organic solvent substantially immiscible towater.

However, the conditions for the solvent effective in the Patent Documentcannot be applied to a solvent somewhat miscible to water. In addition,the applicable monomer needs to be highly oil-soluble or needs to have ahighly oil-soluble alkyl group. Therefore, for a monomer having ahydrophilic substituent such as an alkoxyl group, sufficient functioncannot be expected under the conditions of the polymerization solventand the dopant compound representing a sulfonic acid group.

By the way, the conductive polymer composition can be used for a counterelectrode for a dye-sensitized solar cell and an antistatic film. PatentDocument 10 discloses a counter electrode for a dye-sensitized solarcell having a conductive polymer layer on a plastic film provided with atransparent conductive layer.

In the Patent Document, the conductive polymer layer is formed byapplying a dispersion containing a conductive polymer, and removing thesolvent. However, because the conductive polymer is a layer in whichfine particles are dispersed, and thus the adherence to the transparentconductive layer is low, and thus it is necessary to enhance the surfaceenergy of the transparent conductive layer by plasma treatment or thelike. In addition, polystyrene sulfonic acid is used as a dispersant inExamples of the Patent Document. In this case, there exists a freesulfonic acid which does not contribute to doping of the conductivepolymer, and thus the solvent becomes an aqueous solution. Therefore,when the solution is applied on a film substrate, the range of choice ofthe solvent and the film substrate surface is very broad, and thuspinholes due to nonuniformity of the conductive polymer coating filmeasily occur. In addition, because the polarity of the coating film ishigh due to the remaining sulfonic acid group, the coating film has lowdurability to acetonitrile and an ionic liquid which are commonly usedas a electrolyte solution, and therefore peeling of the coating filmeasily occurs. Because of such causes, there occurs a problem that atransparent conductive film is corroded by iodine in the electrolyte.Therefore, the conductive polymer layer has a problem in the long-termstability as a counter electrode, and thus is insufficient to replace aplatinum counter electrode with.

Furthermore, Patent Document 11 discloses an antistatic film obtained byapplying antistatic material containing a polythiophene compound, acidicpolymer and sugar alcohol on a thermoplastic resin film.

However, in the Patent Document, the antistatic material contains asugar alcohol as an essential component, and thus the transparency andantistatic property of the obtained antistatic film is good. However,because only acidic polymer such as polystyrene sulfonic acid is used asa doping agent to the polythiophene compound, the antistatic filmcontinuously absorbs moisture, and therefore the adherence and theantistatic property can deteriorate, which is problematic.

PRIOR ART REFERENCE Patent Document

-   [Patent Document 1] JP-A-2002-539287-   [Patent Document 2] JP-A-H01-313521-   [Patent Document 3] JP-A-2004-514753-   [Patent Document 4] JP-A-2007-518859-   [Patent Document 5] Japanese Patent No. 2636968-   [Patent Document 6] JP-A-2008-169255-   [Patent Document 7] JP-A-2007-314606-   [Patent Document 8] WO2005/052058-   [Patent Document 9] JP-A-2000-344823-   [Patent Document 10] JP-A-2006-155907-   [Patent Document 11] JP-A-2008-179809

SUMMARY OF THE INVENTION

So, the purpose of the present invention is to provide a conductivepolymer composition which is excellent in solubility to a solvent, andcan be used to form a self-supported film by itself, i.e. a homogeneousmembrane or molded body without pinholes, and a method of manufacturingthe same.

The present inventors have re-tested and researched on theaforementioned prior art to solve the aforementioned problems, andclarified the facts that following factors are necessary from the startof the conductive polymer synthesis to purification and redissolution toa solvent.

<1> It is necessary to use a sufficient amount of an electrolyticsolvent in the polymerization field of a π-conjugated polymer and tostabilize and uniformize an anionic filed during oxidation;

<2> It is necessary to provide a field to control the stacking of theπ-conjugated polymer during polymerization and to supply the monomerstably;

<3> The doping to the π-conjugated polymer proceeds actively in thesepolymerization field;

<4> Precipitation from the initial polymerization field electrolyticsolvent such as water is possible during the doping process;

<5> The stacking of the main chain backbone of the π-conjugated polymerafter the polymerization is prevented by a certain steric molecularhinderance;

<6> The steric hinderance factor itself does not have a tendency to becrystallized, and can be dissolved in a solvent or by heat and so on.

Then, as a result of the further investigation by the present inventors,it was found out that when a polymer compound obtained by copolymerizingspecific monomers is used as an additive upon polymerization of aπ-conjugated polymer, the polymer compound exerts a function as anemulsifier to uniformize the polymerization field, and also exerts afunction as a doping agent, and in addition provides a suitable sterichinderance to the π-conjugated polymer, and thus it is possible toobtain a composite conductive polymer composition which is excellent insolubility to a specific solvent. In addition, the present inventorshave found that the aforementioned conductive polymer composition can beused for a counter electrode for a dye-sensitized solar cell and anantistatic film. Thus, the present invention has been completed.

The present invention provides a composite conductive polymercomposition obtained by doping a π-conjugated polymer (β) with a polymercompound (A); wherein

the polymer compound (A) is obtained by polymerizing the followingcomponents (a-1) to (a-3):

(a-1) a monomer having a sulfonic acid group and a polymerizable vinylgroup in an amount of 20 to 60 mol %,

(a-2) a polar monomer having a hydrophilic group and a polymerizablevinyl group in an amount of 20 to 60 mol %, and

(a-3) a polymerizable monomer other than the components (a-1) and (a-2)in an amount of 20 to 60 mol %; and

the π-conjugated polymer (β) is obtained from a monomer compoundselected from the formulas (I) to (III)

wherein, in the formulas (I) to (III),

at least one of R₁ to R₄ represent an alkoxy group having a carbonnumber of 1 to 10, and the other groups represent a hydrogen atom, analkyl group having a carbon number of 1 to 10, or an alkoxy group havinga carbon number of 1 to 10;

at least one of R₅ and R₆ represent an alkoxy group having a carbonnumber of 1 to 10, and the other group represents a hydrogen atom, analkyl group having a carbon number of 1 to 10 or an alkoxy group havinga carbon number of 1 to 10, or R₅ and R₆ jointly represent analkylenedioxy group having a carbon number of 1 to 8;

R₇ represents a hydrogen atom, an alkyl group having a carbon number of1 to 6, or an aromatic ring group.

Furthermore, the present invention provides a method of method ofmanufacturing a composite conductive polymer composition comprising thesteps of mixing a polymer compound (A) and a compound selected from theaforementioned formulas (I) to (III) in an electrolytic solvent,followed by chemical oxidative polymerization by use of an oxidizingagent; wherein

the polymer compound (A) is obtained by polymerizing the followingcomponents (a-1) to (a-3):

(a-1) a monomer having a sulfonic acid group and a polymerizable vinylgroup in an amount of 20 to 60 mol %,

(a-2) a polar monomer having a hydrophilic group and a polymerizablevinyl group in an amount of 20 to 60 mol %, and

(a-3) a polymerizable monomer other than the components (a-1) and (a-2)in an amount of 20 to 60 mol %.

Furthermore, the present invention provides a composite conductivepolymer composition solution obtained by dissolving the aforementionedcomposite conductive polymer composition in an aromatic solvent, anester-based solvent or a ketone-based solvent in an amount of 0.1 to 10mass %.

Furthermore, the present invention provides a counter electrode for adye-sensitized solar cell obtained from the aforementioned compositeconductive polymer composition.

Furthermore, the present invention provides an antistatic film obtainedfrom the aforementioned composite conductive polymer composition

The composite conductive polymer obtained by polymerization by theeffect of an oxidizing agent in the presence of the polymer compound ofthe invention stably dissolves in an aromatic solvent, an ester-basedsolvent, or a ketone-based solvent.

Therefore, it is possible to easily form a conductive membrane byapplying a solution obtained by dissolving the composite conductivepolymer in a solvent to a portion requiring conductivity, followed byvolatilization of the solvent and drying.

Additional aspects and/or advantages of the invention will be set forthin part in the description which follows and, in part, will be obviousfrom the description, or may be learned by practice of the invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

The polymer compound (A) used in the invention can be manufactured bypolymerizing, according to a common procedure, a component (a-1) monomerhaving a sulfonic acid group and a polymerizable vinyl group, acomponent (a-2) polar monomer having a hydrophilic group and apolymerizable vinyl group, and a component (a-3) polymerizable monomerother than these components in the presence of a polymerizationinitiator.

The component (a-1) monomer having a sulfonic acid group and apolymerizable vinyl group is a monomer having a styrenesulfonic acidgroup, a sulfoethyl group, or like a sulfonic acid group, and examplesthereof include styrenesulfonic acid; sodium styrenesulfonate, potassiumstyrenesulfonate, calcium styrenesulfonate, and like stryrenesulfonatesalts; 2-sulfoethyl(meth)acrylate; and sodium 2-sulfoethyl(meth)acrylate, potassium 2-sulfoethyl(meth)acrylate, calcium2-sulfoethyl(meth)acrylate, and like 2-sulfoethyl(meth)acrylate salts.

The component (a-2) polar monomer having a hydrophilic group and apolymerizable vinyl group is a monomer whose pH is larger than 5.5 andsmaller than 8.0 (5.5<pH<8.0) when the monomer is dissolved indistillated water of pH 7.0 at the room temperature in a concentrationof 0.1 mmol/l. Examples thereof include acrylic acid, methacrylic acid,2-(methacryloyloxy)ethylsuccinic acid, maleic acid (maleic anhydride),2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate,4-hydroxybutyl(meth)acrylate, 2-acetoacetoxyethyl(meth)acrylate,methoxyethyl(meth)acrylate, ethoxyethyl(meth)acrylate,butoxyethyl(meth)acrylate, ethylcarbitol(meth)acrylate,methoxytriethyleneglycol(meth)acrylate,methoxypolyethyleneglycol(meth)acrylate, β-(meth)acryloyloxyethylhydrogen succinate.

Furthermore, examples of the component (a-3) polymerizable monomer otherthan the monomers (a-1) and (a-2) include a monomer having an aromaticgroup or an alicyclic group and a polymerizable vinyl group; and analkyl methacrylate.

Examples of the monomer having an aromatic group or an alicyclic groupand a polymerizable vinyl group include benzyl(meth)acrylate,phenoxyethyl(meth)acrylate, 2-(methyl phthalate)ethyl(meth)acrylate,2-(ethyl phthalate)ethyl(meth)acrylate, cyclohexyl(meth)acrylate,dicyclopentanyl(meth)acrylate, dicyclopentanyloxyethyl(meth)acrylate,dicyclopentenyl(meth)acrylate, dicyclopentenyloxyethyl(meth)acrylate,isobornyl(meth)acrylate, t-butylcyclohexyl(meth)acrylate,cyclohexyl(meth)acrylate, (meth)acrylate morpholine,pentamethylpiperidinyl methacrylate, tetramethylpiperidinylmethacrylate, 1-adamantyl(meth)acrylate,2-methyl-2-adamantyl(meth)acrylate, 2-ethyl-2-adamantyl(meth)acrylate,3-hydroxy-1-adamantyl(meth)acrylate, styrene, dimethylstyrene,naphthalene (meth)acrylate, vinylnaphthalene, vinylpyridine,N-vinylcarbazole, vinyl-N-ethylcarbazole, vinylfluorene.

Examples of the alkyl methacrylate include methyl(meth)acrylate,ethyl(meth)acrylate, n-propyl(meth)acrylate, i-propyl(meth)acrylate,nbutyl(meth)acrylate, i-butyl(meth)acrylate, i-propyl(meth)acrylate,n-pentyl(meth)acrylate, i-pentyl(meth)acrylate, t-butyl(meth)acrylate,2-ethylhexyl(meth)acrylate, isooctyl(meth)acrylate,lauryl(meth)acrylate, stearyl(meth)acrylate.

In manufacturing the polymer compound (A) of the invention, the amountof the component (a-1) is 20 to 60 mol %, and preferably 30 to 40 mol %,the amount of the component (a-2) is 20 to 60 mol %, and preferably 30to 40 mol %, and the amount of the component (a-3) is 20 to 60 mol %,and preferably 30 to 40 mol %.

In manufacturing the polymer compound (A) used for the invention, themolar ratio of the monomer (a-1), the monomer (a-2), and, the monomer(a-3) is important. In other words, the polymer compound of theinvention appropriately balances the emulsifying capacity depending onthe polarity of the respective monomers upon the polymerization of theconductive polymer, the stability of the polymerization of theconductive polymer, the affinity to the conductive polymer backbonewhich influences the doping ratio, and so on, and influences theconductive polymer composition, and makes it soluble to a solvent.

Polymerization of the component (a-1), the component (a-2), and themonomer (a-3) can be performed through a publicly-known method. Forexample, the manufacturing can be performed by mixing the respectivecomponents, and adding a polymerization initiator thereto, andinitiating polymerization by heating, light irradiation and so on.

A polymerization method for manufacturing the aforementioned polymercompound (A) is not in particular limited as long as the method can beperformed in a state that the component (a-2) does not separate from themonomer mixture. Examples of the methods include a solutionpolymerization method, a bulk polymerization method, and a precipitationpolymerization method.

The polymerization initiator used for the polymerization reaction is notin particular limited as long as it is soluble to the aforementionedrespective components and the solvent used in the reaction. Examples ofthe polymerization initiator include benzoyl peroxide (BPO), and likeoil-soluble peroxide thermal polymerization initiators,azobisisobutyronitrile (AIBN), and like oil-soluble azo thermalpolymerization initiators, and azobis-cyano valeric acid (ACVA), andlike water-soluble azo thermal polymerization initiators. When the ratioof water in the solvent of the solution polymerization is large,ammonium persulfate, potassium persulfate, and like water-solubleperoxide thermal polymerization initiators; hydrogen peroxide water, andso on can be used. Furthermore, ferrocene, amines, and like redoxreagents can be used in combination.

The range of use of these polymerization initiators is 0.001 to 0.1 molper 1 mole of the aforementioned compound. The polymerization initiatorcan be used in any of one-time addition, dropwise addition, andsequential addition. Furthermore, in the case of bulk polymerization orsolution polymerization by use of a small amount of a solvent (50 wt %or less with respect to the monomer), a polymerization method by thecombination of mercaptan and metallocene (Patent Document 9) ispossible.

In addition, examples of the solvent used for the aforementionedpolymerization reaction include methanol, ethanol, isopropyl alcohol,butanol, and like alcohol-based solvents; acetone, methyl ethyl ketone,methyl isobutyl ketone, and like ketone-based solvents; methylcellosolve, ethyl cellosolve, propyleneglycol methyl ether,propyleneglycol ethyl ether, and like glycol-based solvents; and methyllactate, ethyl acetate, ethyl lactate, and like ester-based solvents.

Furthermore, a chain transfer agent can be used with the polymerizationinitiator during the polymerization, and the chain transfer agent can beused to adjust the molecular weight. Any chain transfer agent can beused as long as it is soluble to the aforementioned monomer and thesolvent, and examples of the chain transfer agent includedodecylmercaptan, heptylmercaptan, and like alkylthiols;mercaptopropionic acid (BMPA), and like water-soluble thiols each havinga polar group; and α-styrene dimer (ASD), and like lipophilic radicalsuppressants.

Furthermore, the polymerization reaction is preferably performed at atemperature equal to or below the boiling point of the solvent used(except the case of bulk polymerization), for example at approx. 65 deg.C. to 80 deg. C. However, when bulk polymerization or polymerizationperformed by use of mercaptan and metal as in Patent Document 9 isemployed, the polymerization reaction is preferably performed at 25 deg.C. to 80 deg. C.

The thus obtained polymer is purified when necessary to obtain thepolymer compound (A). An example of the purification method is a methodof removing lipophilic low-molecular impurities and an unreactedmonomer, and low-molecular impurities by use of lipophilic poor solventsuch as hexane, and thereafter precipitating the polymer by use ofwater-soluble poor solvent such as acetonitrile or methanol to removethe water-soluble impurities and the residue.

The reason why the purification is preferable is as follows. The polymercompound (A) is introduced into the conductive polymer composition as adoping agent and functions as a stacking suppressant and asolvent-solubilizing agent. Therefore, when a polymerization initiatorresidue, a monomer, an oligomer, an ununiform composition, and so onexist as residues after the polymerization, the function of theconductive polymer composition can deteriorates. Thus, these residuesneed to be removed. Then, as a result of the purification, there isobtained a solubilized state where a nonuniform radical polymer as inPatent Document 7 does not exist, and the composition of the uniformconductive polymer composition and the composition of the polymercompound (A) is uniformly compatibilized.

The GPC weight-average molecular weight of the obtained polymer compound(A) is preferably 3,000 to 100,000. When the weight-average molecularweight is less than 3,000, the function thereof as the polymer compoundis insufficient. In contrast, when it is more than 100,000, thesolubility thereof to the polymerization field (an acid aqueoussolution) during the conductive polymer synthesis can be insufficient,and the solvent solubility of the polymer compound itself can decrease,and provide an adverse influence on the solubilizability of theconductive polymer.

The composite conductive polymer composition of the invention can bemanufactured in the following way by use of the polymer compound (A)obtained by the aforementioned method. That is, the composite conductivepolymer composition obtained by doping, with the polymer compound (A),the π-conjugated polymer (β) comprised of the compound represented bythe formulas (I) to (III) as a monomer component can be obtained bydissolving the aforementioned polymer compound (A) in an electrolyticsolvent; adding, to the obtained solution, the compound, represented bythe formulas (I) to (III), which is a raw material for the π-conjugatedpolymer (β), and oxidizing it by an oxidizing agent.

Among the raw material compounds, the compound represented by theformula (I) is aniline having an alkoxy group as a substituent. Examplesof the compound include o-anisidine, p-anisidine, m-anisidine,methoxyaniline, and butoxyaniline.

Furthermore, the compound represented by the formula (II) is thiophenehaving hydrogen, an alkoxy group or an alkylenedioxy group as asubstituent. Examples of the compound include 3-methoxythiophene,3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene,3,4-dimethoxythiophene, 3,4-(2′,2′-dimethylpropylene)dioxythiophene, and3,4-(2′,2′-diethylpropylene)dioxythiophene.

Furthermore, the compound represented by the formula (III) is pyrrolehaving hydrogen, an alkoxy group or an alkylenedioxy group as asubstituent. Examples of the compound include 3,4-ethylenedioxypyrrole,and 3,4-propylenedioxypyrrole.

One example of the specific method of manufacturing the compositeconductive polymer composition according to the present inventive methodis a method of if necessary, acidifying ion-exchange water which is anelectrolytic solvent; adding the above-obtained polymer compound (A)thereto; adding one or two or more of the raw material compoundsrepresented by the formulas (I) to (III) thereto; and adding anoxidizing agent to cause oxidative polymerization. Depending on thesolubility, of the polymer compound (A), to the ion-exchange water,acetone, methyl ethyl ketone, or like a ketone-based solvent; methanol,ethanol, isopropyl alcohol, or like an alcohol-based solvent; or like anorganic solvent having high hydrophilicity may be used together.

Examples of the acidic component to acidify the electrolytic solvent inthe aforementioned reaction include hydrochloric acid, sulfuric acid,perchloric acid, periodic acid, iron(III) chloride, iron(III) sulfate,and the amount thereof is about 0.5 to 4.0 mol per 1 mol of the compoundof the formulas (I) to (III)

The oxidizing agent used for the reaction needs to be adjusted dependingon the redox potential of the aromatic compound (monomer) forming thecomposite conductive polymer composition. Examples of the oxidizingagent include ammonium peroxodisulfate, potassium peroxodisulfate,sodium peroxodisulfate, iron(III) chloride, iron(III) sulfate, iron(III)tetrafluoroborate, iron(III) hexafluorophosphate, copper(II) sulfate,copper(II) chloride, copper(II) tetrafluoroborate, copper(II)hexafluorophosphate.

The ratio of the polymer compound (A) and the compounds (I) to (III)depends on the property of the finally obtained composite conductivepolymer composition, and thus cannot be simply determined. However, anexample of the preferred range can be represented in the following wayby the molar ratio of the number of the sulfonic acid group in thepolymer compound (A) and the compounds (I) to (III).

That is, the polymer compound (A) may be included in such a way that themolar ratio of the sulfonic acid group in the polymer compound (A) is0.3 to 1.5 per 1 mol of the compound selected from the formulas (I) to(III).

Furthermore, the usage amount of the oxidizing agent is usually about1.0 to 3.0 mol (the value when the oxidizing agent is assumed to bemonovalent) per 1 mol of the compounds (I) to (III). However, dependingon the degree of oxidation (degree of acidity), the usage amount may be1 mol or less per 1 mol of the monomer. Such amount is sufficient forpolymerization.

Furthermore, the preferred range of the temperature for thepolymerization reaction to obtain the composite conductive polymercomposition can vary because the amount of heat generation after theoxidation reaction and the easiness of hydrogen removal depend on thekind of the compounds (I) to (III).

In general, when the compound (I) is used, 40 deg. C. or less ispreferable. When the compound (II) is used, 90 deg. C. or less ispreferable. When the compound (III) is used, 20 deg. C. or less ispreferable.

In order to increase the molecular weight of the composite conductivepolymer composition, the reaction temperature can be lowered and thereaction time can be elongated. In order to decrease the molecularweight, the reaction temperature and time can be changed in the oppositeway.

The thus obtained polymer is, as necessary, subjected to washing and soon, to obtain the composite conductive polymer composition which is thetarget object. As described later, this composition can dissolve in anaromatic solvent, an ester-based solvent and a ketone-based solvent inwhich the conventional conductive polymer composition did not dissolve.

An example of the method of utilizing the thus obtained compositeconductive polymer composition of the invention is to obtain a compositeconductive polymer composition solution by uniformly dissolving thecomposition in an aromatic solvent, an ester-based solvent, or aketone-based solvent. The composite conductive polymer compositionsolution can be used to form an uniform conductive membrane on aspecific portion by applying the composite conductive polymercomposition solution on a portion on which a conductive membrane isdesired to be formed; and volatilizing the solvent in the composition bymeans of drying or the like.

The aforementioned composite conductive polymer composition solution canbe obtained preferably by dissolving the composite conductive polymercomposition in benzene, toluene, xylene, or like an aromatic solvent,ethyl acetate, propyl acetate, butyl acetate, methyl lactate, ethyllactate, or like an ester-based solvent, methyl ethyl ketone,cyclohexanon, cyclopentanone, or like a ketone-based solvent in anamount of about 0.1 to 10 mass %.

Furthermore, the aforementioned composite conductive polymer compositionsolution may further contain benzyl alcohol, phenol, m-cresol, o-cresol,2-naphthol, 1-naphthol, guaiacol, 2,6-dimethylphenol, or like anaromatic compound having a hydroxyl group, in order to improve thestability of the solution and the conductivity in a state of a coatingfilm. These compounds are preferably added in an amount of about 50 to500 parts by weight per 100 parts by weight of the solvent of thecomposite conductive polymer composition solution.

Furthermore, the aforementioned composite conductive polymer compositionsolution may further contain, as a filler component, copper, silver,aluminum, platinum, or like a metal; titanium oxide, indium tin oxide,fluorine-doped tin oxide, alumina, silica, or like a metal oxide;conductive polymer composition, carbon nanotube (CNT), fullerene, carbonblack, or like carbon powder or dispersoid, in order to improve theconductivity of the self-supported film as an antistatic coatingmaterial and improve the catalytic performance thereof as a counterelectrode for a solar cell. These powder or dispersoid is preferablyadded in such a way that the solid content of the powder or dispersoidis about 0.01 to 50 parts by weight per 100 parts by weight of the solidcontent of the composite conductive polymer composition solution.

Furthermore, the aforementioned composite conductive polymer compositioncan be used for an counter electrode for a dye-sensitized solar cell.When transparency is required, the counter electrode for thedye-sensitized solar cell can be formed by laminating the compositeconductive polymer composition on one side of a transparent substrate,or placing a transparent electrode on one side of a transparentsubstrate and laminating the composite conductive polymer composition onthe transparent electrode. When transparency is not required, thecounter electrode can be formed by laminating the composite conductivepolymer composition on a metal foil and so on. The thickness of thecomposite conductive polymer composition is usually in the range of 0.01to 100 μm and preferably in the range of 0.1 to 50 μm.

As the aforementioned transparent substrate, a film or plate having alight transmittance of usually 50% or more, and preferably 80% or moremay be used. Examples of the transparent substrate includes glass, andlike inorganic transparent substrates; polyethylene terephthalate (PET),polycarbonate (PC), polyphenylene sulfide, polysulfone, polyestersulfone, polyalkyl(meth)acrylate, polyethylene naphthalate (PEN),polyether sulfone (PES), polycycloolefin, and like polymer transparentsubstrates. Examples of the metal foil include gold, platinum, silver,tin, copper, aluminum, stainless-steel, nickel, and like metal foils.

The thickness of these transparent substrates is usually in the range of200 to 7000 μm in the case of an inorganic transparent substrate, andusually in the range of 20 to 4000 μm, and preferably 20 to 2000 μm inthe case of a polymer transparent substrate. The thickness is 0.1 μm to1000 μm and preferably 1 μm to 500 μm in the case of a metal foilsubstrate. The polymer transparent substrate and metal foil substratehaving such range of thickness can provide flexibility to the obtaineddye-sensitized solar cell.

When necessary, a transparent electrode may be disposed on one side ofthe aforementioned transparent substrate. Examples of the transparentelectrode used here include a film-shaped conductive metal electrode, amesh-shaped conductive metal electrode.

The aforementioned film-shaped conductive metal electrode is film-shapedand formed of tin oxide, tin-doped indium oxide (ITO), fluorine-dopedtin oxide (FTO) or the like. The film-shaped conductive metal electrodecan by formed by vapor deposition or sputtering of tin oxide, ITO. FTOor the like on the surface of the transparent substrate. The thicknessof the film-shaped conductive metal electrode is usually in the range of0.01 to 1 μm, and preferably in the range of 0.01 to 0.5 μm.

On the other hand, the mesh-shaped conductive metal electrode ismesh-shaped and formed of copper, nickel, aluminum, or like conductivemetal. Specifically, the mesh-shaped conductive metal electrode can beformed by use of copper, nickel, aluminum, or like conductive metaletched, for example by photolithography, to form a mesh having the linewidth of 10 to 70 μm, and preferably 10 to 20 μm and the pitch width ofusually 50 to 300 μm, and preferably 50 to 200 μm. The thickness of theconducting wire of the mesh-shaped conductive metal electrode isapproximately the same as that of the conductive metal used, and isusually in the range of 8 to 150 μm, and preferably 8 to 15 μm. Themesh-shaped conductive metal electrode can be adhered to the surface ofthe transparent substrate by use of adhesive or the like.

In manufacturing the counter electrode of the aforementioneddye-sensitized solar cell, the method of laminating the compositeconductive polymer composition on one side of the aforementionedtransparent substrate or on the transparent electrode disposed on oneside of the transparent substrate is, for example, a method of, one timeor plural times, applying the aforementioned composite conductivepolymer composition solution on one side of the aforementionedtransparent substrate or on the transparent electrode disposed on oneside of the transparent substrate; and removing the solvent in thesolution.

The aforementioned composite conductive polymer composition solution canbe applied by use of a dip coater, a micro bar coater, a roll coater, acomma coater, a die coater, a gravure coater, or like a publicly-knowncoater.

The solvent may be removed by use of natural drying by leaving as it is,forced drying under heating conditions by hot-air or infrared light, orlike method.

The aforementioned counter electrode for the dye-sensitized solar cellis excellent in productivity in that the aforementioned compositeconductive polymer composition used for the counter electrode is solubleto an organic solvent, and thus is easier to be applied than adispersion liquid in which a conventional composite conductive polymercomposition is dispersed in an aqueous medium. Furthermore, it ispossible to suppress corrosion deterioration which is caused by the acidaqueous solution in the counter electrode preparation stage.

Furthermore, the aforementioned counter electrode for the dye-sensitizedsolar cell is excellent in adhesion to the aforementioned transparentsubstrate, transparent electrode, and metal foil and thus can be usedfor a long time because the aforementioned composite conductive polymercomposition used for the electrode uses the polymer compound (A)obtained by copolymerizing the aforementioned component (a-1), component(a-2) and component (a-3) in a predetermined range.

Furthermore, the aforementioned counter electrode for the dye-sensitizedsolar cell can be used for a long time because the use of the polymercompound (A) in the aforementioned composite conductive polymercomposition, with reduced degree of acidity, obtained by copolymerizingthe aforementioned component (a-1), component (a-2) and component (a-3)in a predetermined range suppresses corrosion of the transparentelectrode (conductive metal) and improves durability to the electrolyte.

In addition, the aforementioned counter electrode for the dye-sensitizedsolar cell can be supplied at a low price because the use of thecomposite conductive polymer film as an uniform oxidation resistancefilm enables the use of various metals. This is in contrast to the priorart in which an expensive platinum electrode has been used as anelectrode having oxidation resistance to the electrolyte.

Furthermore, by use of the aforementioned composite conductive polymercomposition, it is possible to manufacture an antistatic film having lowresistance because the aforementioned composite conductive polymercomposition can be used to form a self-supported film by coating anddrying by itself. In addition, when the composite conductive polymercomposition is mixed with thermoplastic resin and/or thermosetting resinas necessary, the antistatic film can be obtained by (1) a method ofmelting-kneading the material by use of an extruder; and forming a filmfrom the material by use of a T-die, or (2) a method of applying theaforementioned composite conductive polymer composition solution on oneside or both sides of a film of thermoplastic resin, thermosettingresin, and glass; and removing the solvent in the solution to form anantistatic layer.

Examples of the thermoplastic resin used in the aforementionedantistatic film include polyolefin, polyvinyl chloride, polyvinylidenechloride, polystyrene, polyvinyl acetate, polytetrafluoro-ethylene,polyacrylonitrile-butadiene-styrene, polyacrylonitrile-styrene,polymethacryl, polyacryl, saturated polyester, polyamide, polycarbonate,modified polyphenylene ether, polyphenylene sulfide, polysulfone,polyarylate, liquid crystal polymer, polyether ether ketone, andpolyamide-imide. Polymer alloy of these thermoplastic resins andthermoplastic elastomer are also included.

Examples of the thermosetting resin used in the aforementionedantistatic film include polyphenol, polyepoxy, unsaturated polyester,polyurethane, polyimide, polyurea, silicone resin, melamine resin,fluorine resin, alkyd resin.

Furthermore, it is possible to form an antistatic film with reducedvariation in the property under various environmental conditions withhigh or low humidity and high transparency by use of the polymercompound (A) obtained by copolymerizing the aforementioned component(a-1), component (a-2) and component (a-3) in a predetermined range.

EXAMPLES

The present invention will be explained in more detail with reference tothe following Examples, but the present invention is not limited bythese Examples. The molecular weight and surface resistance value in theExamples and Comparative Examples are measured in the following way.

<Molecular Weight>

The molecular weight was measured by GPC under the following conditions.

Apparatus Name: HLC-8120 (manufactured by Tosoh Corporation)

Column: GF-1G7B+GF-510HQ (ASAHIPAK® a registered trademark of ShowaDenko K.K.) (ASAHIPAK is a hard gel vinyl alcohol copolymer used forhigh performance liquid chromatography columns).

Reference Material: polystyrene and sodium polystyrenesulfonate

Sample Concentration: 1.0 mg/ml

Eluent: 50 millimole lithium chloride aqueous solution/CH₃CN=60/40 wt

Flow Rate: 0.6 ml/min

Column Temperature: 30 deg. C.

Detector: UV254 nm

<Surface Resistance>

The surface resistance was measured by use of Low Resistivity MeterLoresta GP, PSP type probe manufactured by Dia Instruments Co., Ltd. andby the four-terminal four-probe method.

Synthesis Example 1 Polymerization of Polymer Compound

Styrenesulfonic acid (NaSS) (25 g), 2-hydroxyethyl methacrylate (2-HEMA)(20 g), phenoxyethyl methacrylate (PEMA) (55 g), ion-exchange water (100g), isopropyl alcohol (IPA) (100 g), methyl ethyl ketone (MEK) (150 g)were added to a four-neck flask with a volume of 1000 cm³ and having astirrer, a nitrogen gas introducing tube, a reflux condenser, an inletand a thermometer. While introducing nitrogen gas into the flask, andthe mixture in the flask was heated to 70 deg. C. Thereafter,azobisisobutyronitrile (0.3 g) was added to the flask, and thepolymerization reaction was conducted for 18 hours at 70 deg. C. toobtain a polymer solution (A-1).

Synthesis Example 2 Polymerization of Polymer Compound

The polymer solutions (A-2 to 14) were obtained by the method of thepolymerization of the polymer compound as in Synthesis Example 1 exceptthat the monomer and the polymerization solvent were changed as shown inTable 1. The polymer solution (A-1) obtained in Synthesis Example 1 isalso shown in Table 1.

TABLE 1 Polymerization Polymer Monomer Composition Medium CompositionSolution Nass 2-HEMA 2-EHMA PEMA FA-513M Water IPA  MEK A-1 25 20 (25) —55 — 100 100 150 (20) (55) A-2 28 51 (60) — 21 — 100 200 — (20) (20) A-326 33 (40) — 41 — 100 100 150 (20) (40) A-4 64 14 (20) — 18 — 150 200 —(60) (20) A-5 42 15 (20) — 43 — 100 100 150 (35) (45) A-6 44 36 (45) —20 — 150 200 — (35) (20) A-7 25 20 (26) 29 (25) 26 — 100 100 150 (21)(28) A-8 24 22 (31) 30 (28) — 24 (20) 100 150 150 (21) A-9 19 21 (26) —60 — 100 100 150 (15) (59) A-10 77 14 (20) —  9 — 100 200 — (70) (10)A-11 57  7 (10) — 36 — 100 150 150 (50) (40) A-12 28 61 (70) — 11 — 100200 — (20) (10) A-13 13 16 (20) — 71 — 100 150 150 (10) (70) A-14 19 12(15) — 69 — 100 150 150 (15) (70)

In Table 1, Nass represents styrenesulfonic acid, 2-HEMA represents2-hydroxyethyl methacrylate, 2-EHMA represents 2-ethylhexyl acrylate,PEMA represents phenoxyethyl methacrylate, FA-531M representsdicyclopentenyl methacrylate (FANCRYL (registered trademark) FA-513M,manufactured by Hitachi Chemical Co., Ltd.). Values in Table 1 representmass %, and values in the parathesis of Table 1 represent molarfraction.

Synthesis Example 3 Purification of Polymer Compound

The polymer compound powder AP-1 to 14 were obtained by one of themethods shown below from the polymer solution A-1 to 14 obtained inSynthesis Examples 1 and 2. The weight-average molecular weight (Mw) ofthe obtained powder measured by the gel permeation chromatography (GPC)is shown in Table 2.

[Purification Method A]

The total amount of the obtained polymer solution was moved to a 2000cm³ beaker, and acetone (600 g) was added thereto while stirring by astirrer, and thereafter the stirring was stopped to obtain aprecipitate. The precipitate was subjected to filtration under reducedpressure, and the residue was dried for 24 hours at 100 deg. C. by useof a dryer, followed by pulverization by use of a mortar, to obtainpowder of the polymer compound.

[Purification Method B]

The total amount of the obtained polymer solution was moved to a 2000cm³ beaker, and IPA (600 g) was added thereto while stirring by astirrer, and thereafter the stirring was stopped to obtain aprecipitate. The precipitate was subjected to filtration under reducedpressure, and the residue was dried for 24 hours at 100 deg. C. by useof a dryer, followed by pulverization by use of a mortar, to obtainpowder of the polymer compound.

[Purification Method C]

The total amount of the obtained polymer solution was moved to a 2000cm³ beaker, and ion-exchange water (100 g) and hexane (500 g) were addedthereto while stirring by a stirrer, and thereafter the mixture was leftstill for 1 hour and a hexane layer containing impurities was removed.The solution in the aqueous layer side was moved to an evaporator, andIPA was distilled away. Again, the total amount of the remaining liquidwas moved to a 2000 cm³ beaker, and acetone (400 g) was added theretowhile stirring by a stirrer. Thereafter, the stirring was stopped toobtain a precipitate. The precipitate was subjected to filtration underreduced pressure, and the residue was dried for 24 hours at 100 deg. C.by use of a dryer, followed by pulverization by use of a mortar, toobtain powder of the polymer compound.

TABLE 2 Polymer Solution Purification Method Mw AP-1 A-1 A 50,000 AP-2A-2 A 41,000 AP-3 A-3 A 45,000 AP-4 A-4 B 40,000 AP-5 A-5 A 44,000 AP-6A-6 B 44,000 AP-7 A-7 A 42,000 AP-8 A-8 A 44,000 AP-9 A-9 A 47,000 AP-10A-10 C 38,000 AP-11 A-11 C 42,000 AP-12 A-12 C 39,000 AP-13 A-13 A44,000 AP-14 A-14 A 43,000

Example 1

The polymer compound (AP-1) (3.3 g) which was obtained in SynthesisExample 3, ion-exchange water (500 g), 25% hydrochloric acid aqueoussolution (1.46 g) was added to a four-neck flask with a volume of 1000cm³ and having a stirrer, a nitrogen gas introducing tube, a refluxcondenser, an inlet and a thermometer. The mixture was heated to 60 deg.C., and was stirred for 3 hours, and thereafter was cooled to 25 deg. C.The solution in the flask was uniform and transparent.

After that, 3,4-ethylenedioxythiophene (1.42 g) was added to thesolution in the flask, and the mixture was stirred to obtain an uniformemulsified liquid, and thereafter heated to 80 deg. C. Then, 14.3 g ofiron(III) sulfate n-hydrate was added to the flask, and thepolymerization reaction was continued for 48 hours at 80 deg. C.

After the polymerization reaction, the total amount of the reactionsolution was filtered under reduced pressure, and the residue was movedto a 500 cm³ beaker, and thereafter acetonitrile (100 g) andion-exchange water (100 g) were added thereto, and then the resultantmixture was stirred for 30 minutes, and was subjected to filtrationunder reduced pressure. The residues were dried under reduced pressurefor 24 hours at 70 deg. C., to obtain a composite conductive polymercomposition (E-1).

Example 2

The polymer compound (AP-2) (2.95 g) which was obtained in SynthesisExample 3, ion-exchange water (500 g), 25% hydrochloric acid aqueoussolution (1.46 g) was added to a four-neck flask with a volume of 1000cm³ and having a stirrer, a nitrogen gas introducing tube, a refluxcondenser, an inlet and a thermometer. The mixture was heated to 60 deg.C., and was stirred for 3 hours, and thereafter was cooled to 25 deg. C.The solution in the flask was uniform and transparent.

After that, 3,4-ethylenedioxythiophene (1.42 g) was added to thesolution in the flask, and the mixture was stirred to obtain an uniformemulsified liquid, and thereafter heated to 80 deg. C. Then, 4.1 g ofiron(III) chloride was dissolved in ion-exchange water (30 g), and thesolution was dripped over 2 hours in the flask at 80 deg. C. After thedripping, the polymerization reaction was continued for 48 hours at 80deg. C.

After the polymerization reaction, the total amount of the reactionsolution was filtered under reduced pressure, and the residue was movedto a 500 cm³ beaker, and thereafter ion-exchange water (100 g) wereadded thereto, and then the resultant mixture was stirred for 30minutes, and was subjected to filtration under reduced pressure. Theseprocedures were repeated two more times, and thereafter the residue wasmoved to a 500 cm³ beaker and acetonitrile (100 g) was added thereto,and then the resultant mixture was stirred for 30 minutes, and wassubjected to filtration under reduced pressure. The residues were driedunder reduced pressure for 24 hours at 70 deg. C., to obtain a compositeconductive polymer composition (E-2).

Example 3

The composite conductive polymer composition (E-3) was obtained in thesame way as in Example 2 except that the polymer compound (AP-2) (2.95g) was replaced with the polymer compound (AP-3) (3.17 g).

Example 4

The composite conductive polymer composition (E-4) was obtained in thesame way as in Example 2 except that the polymer compound (AP-2) (2.95g) was replaced with the polymer compound (AP-4) (1.29 g) andion-exchange water (500 g) was replaced with ion-exchange water (400 g)and 25 deg. C. saturated saline (100 g).

Example 5

The composite conductive polymer composition (E-5) was obtained in thesame way as in Example 2 except that the polymer compound (AP-2) (2.95g) was replaced with the polymer compound (AP-5) (1.96 g).

Example 6

The composite conductive polymer composition (E-6) was obtained in thesame way as in Example 2 except that the polymer compound (AP-2) (2.95g) was replaced with the polymer compound (AP-6) (1.87 g).

Example 7

The polymer compound (AP-7) (3.30 g) which was obtained in SynthesisExample 3, ion-exchange water (500 g), 25% hydrochloric acid aqueoussolution (1.46 g) was added to a four-neck flask with a volume of 1000cm³ and having a stirrer, a nitrogen gas introducing tube, a refluxcondenser, an inlet and a thermometer. The mixture was heated to 60 deg.C., and was stirred for 3 hours, and thereafter was cooled to 25 deg. C.The solution in the flask was uniform and transparent.

After that, o-anisidine (1.23 g) was added to the solution in the flask,and the mixture was stirred to obtain an uniform emulsified liquid, andthereafter cooled to 0 deg. C. Then, 3.00 g of ammonium persulfate wasdissolved in ion-exchange water (30 g), and the solution was drippedover 2 hours in the flask at 0 deg. C. After the dripping, thepolymerization reaction was continued for 48 hours at 0 deg. C.

After the polymerization reaction, the total amount of the reactionsolution was filtered under reduced pressure, and the residue was movedto a 500 cm³ beaker, and thereafter ion-exchange water (100 g) wereadded thereto, and then the resultant mixture was stirred for 30minutes, and was subjected to filtration under reduced pressure. Theseprocedures were repeated two more times, and thereafter the residue wasmoved to a 500 cm³ beaker and acetonitrile (100 g) was added thereto,and then the resultant mixture was stirred for 30 minutes, and wassubjected to filtration under reduced pressure. The residues were driedunder reduced pressure for 24 hours at 70 deg. C., to obtain a compositeconductive polymer composition (E-7).

Example 8

The composite conductive polymer composition (E-8) was obtained in thesame way as in Example 7 except that the polymer compound (AP-7) (3.30g) was replaced with the polymer compound (AP-8) (3.43 g) ando-anisidine 1.23 g was replaced with 3,4-ethylenedioxypyrrole (1.25 g).

Comparative Example 1

The comparative conductive polymer composition (C-1) was obtained in thesame way as in Example 2 except that the polymer compound (AP-2) (2.95g) was replaced with the polymer compound (AP-9) (4.34 g).

Comparative Example 2

Polymerization was performed in the same way as in Example 2 except thatthe polymer compound (AP-2) (2.95 g) was replaced with the polymercompound (AP-10) (1.07 g).

After the polymerization reaction, no solid precipitate was found fromthe polymerization solution. So, the total amount of the reactionsolution was moved to an evaporator, and the reaction solution washeated and distilled under reduced pressure so as to reduce the volumeto 50 g. Then, insoluble substances precipitated in the reactionsolution. The resultant reaction solution was filtered under reducedpressure. Then, the residue was moved to a 200 cm³ beaker, ion-exchangewater (50 g) was added thereto, and then the resultant mixture wasstirred for 30 minutes, and was subjected to filtration under reducedpressure. Such water washing and filtration under reduced pressure wasconducted one more time, and the residue was moved to a 200 cm³ beaker,and n-hexane (50 g) was added thereto, and the mixture was stirred for30 minutes, and was subjected to filtration under reduced pressure. Theresidues were dried under reduced pressure for 24 hours at 70 deg. C.,to obtain the comparative composite conductive polymer composition(C-2).

Comparative Example 3

The comparative conductive polymer composition (C-3) was obtained in thesame way as in Example 2 except that the polymer compound (AP-2) (2.95g) was replaced with the polymer compound (AP-11) (1.44 g).

Comparative Example 4

The comparative conductive polymer composition (C-4) was obtained in thesame way as in Example 2 except that the polymer compound (AP-2) (2.95g) was replaced with the polymer compound (AP-12) (2.94 g).

Comparative Example 5

The comparative conductive polymer composition (C-5) was obtained in thesame way as in Example 2 except that the polymer compound (AP-2) (2.95g) was replaced with the polymer compound (AP-13) (6.34 g).

Comparative Example 6

The comparative conductive polymer composition (C-6) was obtained in thesame way as in Example 2 except that the polymer compound (AP-2) (2.95g) was replaced with the polymer compound (AP-14) (4.34 g).

Examples 9 to 16 and Comparative Examples 7 to 12

Preparation and Evaluation of Conductive Polymer Composition Solution

The composite conductive polymer composition obtained in Examples 1 to 8and the comparative conductive polymer composition obtained inComparative Examples 1 to 6 (E-1 to 8, C-1 to 6) (2 g) and the solventshown in Table 3 below were added to a 200 cm³ beaker, and they werestirred and dissolved at room temperature to obtain a conductive polymercomposition solution. The compositions C1 to C6 (Comparative Examples 7to 12) did not dissolve in any one of the five kinds of solvents shownin Table 3, and did not dissolve in the mixture solvent thereof, andthus they existed in a micro-dispersion state.

Thereafter, the conductive polymer composition solution ormicro-dispersion was applied on a glass substrate by use of a doctorblade so that the thickness after drying was 10 μm, and dried. The stateof the film and the measured surface resistance are shown in Table 4.

TABLE 3 Conductive Polymer Solvent Composition To IPA MeOH EtAc MEKState of Solution Ex. 9 E-1 91 9 — — — Blackish Green Uniform SolutionEx. 10 E-2 91 — 9 — — Blackish Green Uniform Solution Ex. 11 E-3 91 9 —— — Blackish Green Uniform Solution Ex. 12 E-4 — — 9 — 91 Blackish GreenUniform Solution Ex. 13 E-5 — — 9 91 — Blackish Green Uniform SolutionEx. 14 E-6 — — 9 — 91 Blackish Green Uniform Solution Ex. 15 E-7 91 — 9— — Blackish Red Uniform Solution Ex. 16 E-8 91 9 — — — Black UniformSolution Comp. Ex. 7 C-1 91 9 — — — Black Micro-Dispersion Comp. Ex. 8C-2 91 9 — — — Black Micro-Dispersion Comp. Ex. 9 C-3 91 9 — — — BlackMicro-Dispersion Comp. Ex. 10 C-4 91 9 — — — Black Micro-DispersionComp. Ex. 11 C-5 91 9 — — — Black Micro-Dispersion Comp. Ex. 12 C-6 91 9— — — Black Micro-Dispersion

In Table 3, To represents toluene. IPA represents isopropyl alcohol.MeOH represents methyl alcohol. EtAC represents methyl acetate, and MEKrepresents methyl ethyl ketone.

TABLE 4 Film Resistance (/□) State of Coating Film Ex. 9  15 kΩ BlackishGreen Uniform Coating Film Ex. 10  15 kΩ Blackish Green Uniform CoatingFilm Ex. 11  30 kΩ Blackish Green Uniform Coating Film Ex. 12  25 kΩBlackish Green Uniform Coating Film Ex. 13  15 kΩ Blackish Green UniformCoating Film Ex. 14  20 kΩ Blackish Green Uniform Coating Film Ex. 15200 kΩ Blackish Red Uniform Coating Film Ex. 16 350 kΩ Black UniformCoating Film Comp. Ex. 7  10 MΩ or larger Black Irregular Film Comp. Ex.8  10 MΩ or larger Black Irregular Film Comp. Ex. 9  10 MΩ or largerBlack Irregular Film Comp. Ex.  10 MΩ or larger Black Irregular Film 10Comp. Ex.  10 MΩ or larger Black Irregular Film 11 Comp. Ex.  10 MΩ orlarger Black Irregular Film 12

Example 17 to Example 23 and Comparative Example 13 to ComparativeExample 15

A dye-sensitized solar cell element was manufactured by replacing thecounter electrode (copper mesh electrode having openings) and thecounter electrode substrate (PET film having a thickness of 80 μm) usedin Example 1 of International Publication WO/2009/013942 with a productobtained by applying the composite conductive polymer compositionsolution prepared in Examples 1 to 4 or the conductive polymercomposition solution prepared in Comparative Examples 2 by use of adoctor blade on a SUS foil, an ITO PEN film, a glass substrate, an ITOglass substrate or a FTO glass substrate so that the thickness afterdrying was 5 μm.

The evaluation of the obtained dye-sensitized solar cell element wasperformed by use of a solar simulator YSS-80A manufactured by YamashitaDenso Corporation. The short-circuit current, open voltage, fill factorand power generation efficiency of the cell was evaluated byinvestigating the I-V characteristic under AM1.5 (1sun;100 mW/cm²)irradiation to an element having a cell area of 1 cm². The result wasshown in Table 1.

TABLE 5 Short- Power Circuit Open Fill Generation Counter Electrode andCurrent Voltage Factor Efficiency Counter Electrode Substrate (Jsc/mA)(Voc/V) (FF) (Eff/%) Ex. 17 ITO Glass Substrate + 5.0 0.78 60 2.3Composite Conductive Polymer Composition of Ex. 1 Ex. 18 ITO GlassSubstrate + 2.8 0.74 63 1.3 Composite Conductive Polymer Composition ofEx. 2 Ex. 19 SUS Foil + 1.7 0.76 45 1.7 Composite Conductive PolymerComposition of Ex. 3 Ex. 20 ITO glass substrate + 3.2 0.76 64 1.6Composite Conductive Polymer Composition of Ex. 4 Ex. 21 FTO GlassSubstrate + 3.2 0.76 64 1.6 Composite Conductive Polymer Composition ofEx. 1 Ex. 22 ITO PEN Film + 2.6 0.80 48 1.0 Composite Conductive PolymerComposition of Ex. 1 Ex. 23 Glass Substrate + 1.1 0.74 67 0.5 CompositeConductive Polymer Composition of Ex. 1 Comp. ITO Glass Substrate + 1.30.80 10 0.1 Ex. 13 Conductive Polymer Composition of Comp. Ex. 2 Comp.ITO Glass Substrate 1.3 0.56 7 0.05 Ex. 14 Comp. FTO Glass Substrate 1.30.56 7 0.05 Ex. 15

As shown above, the dye-sensitized solar cell element obtained by use ofthe composite conductive polymer composition of the invention exhibitedhigh photoelectric conversion efficiency.

Example 24 to Example 25 and Comparative Example 16 to ComparativeExample 17

An antistatic film was manufactured by adjusting, to 2.5%, the solidcontent of the composite conductive polymer composition solutionprepared in Examples 1 to 2, and the conductive polymer compositionsolution prepared in Comparative Examples 4 to 5, and applying theadjusted solution on a glass substrate having a thickness of 1000 μm anda PET film substrate having a thickness of 100 μm, and removing thesolvent by use of a hot-air dryer to form an antistatic layer. Thethicknesses of the antistatic layers measured by Stylus Surface Profiler(Dektak 6 M: manufactured by ULVAC) were all approx. 25 nm.

The surface resistance value of the obtained antistatic film wasmeasured after leaving the antistatic film in the following conditions.The evaluations results are shown in Table 2.

TABLE 6 Glass Substrate PET Film Substrate Condition (1) Condition (2)Condition (1) Condition (2) UP: State of Film DOWN: Surface ResistanceAntistatic Film (Ω/□) Ex. 24 Composite ∘ ∘ ∘ ∘ Conductive 3.33 × 1083.20 × 108 9.45 × 108 1.02 × 109 Polymer Composition of Ex. 1 Ex. 25Composite ∘ ∘ ∘ ∘ Conductive 4.20 × 108 4.49 × 108 1.25 × 109 1.33 × 109Polymer Composition of Ex. 2 Comp. Conductive >1.00 × 1015 >1.00 ×1015 >1.00 × 1015 >1.00 × 1015 Ex. 16 Polymer Composition of Comp. Ex. 5Comp. Conductive ∘ >1.00 × 1015 ∘ >1.00 × 1015 Ex. 17 Polymer 2.30 × 1084.41 × 108 Composition of Comp. Ex. 4 Dissolved in Water Conditions (1):192 hours at 23 deg. C. and 50% RH Conditions (2): 168 hours at 40 deg.C. and 80% RH

As shown above, the antistatic film of the invention exhibitedsufficient antistatic property even when it is used in hot and humidconditions.

INDUSTRIAL APPLICABILITY

The composite conductive polymer composition of the invention use, as adoping agent, the polymer compound (A) comprised of three components of(a-1) a monomer having a sulfonic acid group and a polymerizable vinylgroup, (a-2) a monomer having a polar group, and (a-3) a polymerizablemonomer other than the components (a-1) and (a-2), and thus is stablysoluble to an aromatic, ester-based, or ketone-based solvent or thelike.

Furthermore, the thus-obtained composite conductive polymer compositionis dissolved in an alcohol-based, glycol-based, or ether-based solventin a transparent state to obtain a composite conductive polymercomposition solution. This solution can be used to easily form aconductive membrane on a portion which requires conductivity, and thuscan be used extremely advantageously in the field of electroniccomponents and so on.

Furthermore, an electrode for a dye-sensitized solar cell and anantistatic film obtained from the composite conductive polymercomposition of the invention have excellent performance.

Although a few embodiments of the present invention have been shown anddescribed, it would be appreciated by those skilled in the art thatchanges may be made in this embodiment without departing from theprinciples and spirit of the invention, the scope of which is defined inthe claims and their equivalents.

What is claimed is:
 1. A composite conductive polymer compositionobtained by doping a π-conjugated polymer (β) with a polymer compound(A); wherein the polymer compound (A) is obtained by polymerizing thefollowing components (a-1) to (a-3), the sum of the components (a-1) to(a-3) being 100 mol %: (a-1) a monomer having a sulfonic acid group anda polymerizable vinyl group in an amount of 20 to 60 mol %, (a-2) apolar monomer having a hydrophilic group and a polymerizable vinyl groupand not having a sulfonic acid group in an amount of 20 to 60 mol %, and(a-3) a polymerizable monomer other than the components (a-1) and (a-2)in an amount of 20 to 60 mol %; and the π-conjugated polymer (β) isobtained from a monomer compound selected from the formulas (I) to (III)

wherein, in the formulas (I) to (III), at least one of R₁ to R₄represent an alkoxy group having a carbon number of 1 to 10, and theother groups represent a hydrogen atom, an alkyl group having a carbonnumber of 1 to 10, or an alkoxy group having a carbon number of 1 to 10;at least one of R₅ and R₆ represent an alkoxy group having a carbonnumber of 1 to 10, and the other group represents a hydrogen atom, analkyl group having a carbon number of 1 to 10 or an alkoxy group havinga carbon number of 1 to 10, or R₅ and R₆ jointly represent analkylenedioxy group having a carbon number of 1 to 8; R₇ represents ahydrogen atom, an alkyl group having a carbon number of 1 to 6, or anaromatic ring group, wherein the component (a-2) is a monomer producinga solution whose pH is larger than 5.5 and smaller than 8.0 (5.5<pH<8.0)when the monomer is dissolved in distillated water of pH 7.0 at the roomtemperature in a concentration of 0.1 mmol/l, and wherein the component(a-2) polar monomer having a hydrophilic group and a polymerizable vinylgroup is selected from acrylic acid, methacrylic acid,2-(methacryloyloxy)ethylsuccinic acid, maleic acid (maleic anhydride),2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,4-hydroxybutyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate,methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethyl(meth)acrylate, ethylcarbitol (meth)acrylate, methoxytriethyleneglycol(meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, andβ-(meth)acryloyloxyethyl hydrogen succinate.
 2. The composite conductivepolymer composition of claim 1, wherein the component (a-1) monomerhaving a sulfonic acid group and a polymerizable vinyl group is selectedfrom the group consisting of sodium styrenesulfonate, styrenesulfonicacid, sodium 2-sulfoethyl (meth)acrylate and 2-sulfoethyl(meth)acrylate.3. The composite conductive polymer composition of claim 1, wherein thecomponent (a-3) polymerizable monomer other than the components (a-1)and (a-2) is a monomer having an aromatic group or an alicyclic groupand a polymerizable vinyl group.
 4. The composite conductive polymercomposition of claim 1, wherein the component (a-3) polymerizablemonomer other than the components (a-1) and (a-2) is a monomer having anaromatic group or an alicyclic group and a polymerizable vinyl group,which is selected from the group consisting of benzyl (meth)acrylate,phenoxyethyl (meth)acrylate, neopentyl glycol acrylate benzoate ester,cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl(meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate,t-butylcyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate,dicyclopentenyloxyethyl (meth)acrylate, pentamethylpiperidinyl(meth)acrylate, tetramethylpiperidinyl (meth)acrylate, 1-adamantyl(meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, vinylpyridine and(meth)acryloyloxy morpholine.
 5. The composite conductive polymercomposition of claim 1, wherein the component (a-3) polymerizablemonomer other than the components (a-1) and (a-2) is analkyl(meth)acrylate.
 6. The composite conductive polymer composition ofclaim 1, wherein the component (a-3) polymerizable monomer other thanthe components (a-1) and (a-2) is an alkyl (meth)acrylate selected fromthe group consisting of methyl (meth)acrylate, ethyl (meth)acrylate,n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl(meth)acrylate, i-butyl (meth)acrylate, i-propyl (meth)acrylate, t-butyl(meth)acrylate, n-pentyl (meth)acrylate, i-pentyl (meth)acrylate,2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, lauryl(meth)acrylate and stearyl (meth)acrylate.
 7. A composite conductivepolymer composition solution obtained by dissolving the compositeconductive polymer composition of claim 1 in an aromatic solvent,ester-based solvents or ketone-based solvent in an amount of 0.1 to 10mass %.
 8. The composite conductive polymer composition solution ofclaim 7, further comprising metal, oxidation metal, conductive polymercomposition, carbon powder or dispersoid.
 9. A counter electrode for adye-sensitized solar cell obtained from the composite conductive polymercomposition of claim
 1. 10. An antistatic film obtained from thecomposite conductive polymer composition of claim 1.